Indandione dyes



United States Patent Ofi ice 3,153,643 WDANDI'UNE DYES- Ernest Merian,Bottmingen, Easel-Land, and ditto Senn, Arlesheim, Basel-Land,Switzerland, assignor to Sandoz Ltd, Basel, Witzerland No Drawing. FiledJune '7, 1960, Ser. No. 34553 Claims priority, application Switzerland,June 22, 1950, 75,044; Nov. 153, 1959, 80,755 4 (Ilaims. (ill. 260--193) The present invention relates to indandione dyestufis of theformula wherein x represents hydrogen or halogen,

y represents hydrogen, when x is halogen, and it represents hydrogen orhalogen, when x is hydrogen,

z represents halogen, when y represents halogen, and when y is hydrogen,it represents halogen, the nitro or the cyano group,

and the phenylene nucleus A may contain non-Watersolubilizingsubstituents.

The process for their production consists in coupling 1 mol of the diazocompound of an amine of the formula wherein x, y and 2 have the abovenamed meanings, with 1 mol of a 1,3-indandione which may containnon-watersolubilizing substituents in the phenylene nucleus or with 1mol of a compound which is converted into a 1,3-

indandione under the operating conditions employed.

The coupling reaction is effected in acid, neutral or alkaline medium atlow temperatures, e.g. 5 to 15 C. Diazo components which are Worthspecial mention are the amines:

l-amino-2-chloro-4-methylsulfonylbenzene,1-amino-2-nitro-4-methylsulfonylbenzene,l-amino-2.5-dichloro-4-methylsulfonylbenzene,l-amino-2-chloro-6-nitro-4-methylsulfonylbenzene,1-amino-2-bromo-4-methylsulfonylbenzene.

Examples of suitable coupling components, other than 1.3-indandioneitself, are monochloro-l.3-indandione, 5. 6 dichloro 1.3 indandione,2-substituted indandiones which under the conditions of applicationexchange their radical in the 2-position for a phenylazo radical, e.g.1.3- indandione-Z-carboxylic acid and its alkyl esters.

The indandione dyestufis are brought into a finely divided form bydissolving in a water-miscible solvent, if necessary at elevatedtemperature, and running the solution into water, upon which the productis filtered off, washed and kneaded with a dispersing agent. The pasteformed can be dried at normal or reduced pressure or by nozzle drying.Another methodof converting the dyestuifs into a finely divided form isto grind or knead them in the dry or moist state in presence ofdispersing agents and if necessary fillers and/or grinding assistants toreduce the particle size, the dyestufi then being dried by one of thedrying processes employed in pigment manufacture. The dyestuifpreparations thus obtained contain the indandione dyestuffs in particlesof the order of magnitude of La.

In certain cases the afiinity of the dyestuif preparations can beimproved by mixing two or more dyestuffs which have been converted intothe finely divided form.

.The indandione dyestuffs disclosed herein are suitable for dyeing,padding and printing polyester fibers, in particular the condensationproducts of terephthalic acid and ethylene glycol which are marketedunder the trade names Dacron, Dacron 64, Terylene, Tergal, Terital,Trevira, Kodel, Teron, Fortrel, Vycron, Lanon and Diolen; further thecellulose ester fibers: secondary cellulose acetate and cellulosetriacetate; and the synthetic polyamide fibers (nylon 66 and the typesmarketed under the trade names Perlon, Mirlon, Grilon and Rilsan) Theyellow to orange dyeings, paddings and prints obtained on polyesterfibers are notable for their good fastness to light, sublimation andheat setting and their very good washing and perspiration fastness. Thedyestulls reserve Wool, cotton and viscose in blended fabrics. Thislast-mentioned property has become very important as a result of thewide variety of blended fabrics now produced, especially those composedof a polyester fiber and wool. When blended fabrics of this type aredyed with disperse dyestulis the wool is stained to a considerable depthand as the stain is not fast the goods lose in value. There are nocommercially available yellow disperse dyestuffs which give asuificiently good reserve of wool. A number of the indandione dyestufisof the present invention are superior to all the known commercialdyestuiis in this respect. 7

Another advantage of the new dyestuffs is their excellent stabilityagainst hydrolysis in Water up to C. and in the dry state up to 250 C.Most of the greenish yellow dyestuffs of shade are more or lessdecomposed when dyed under pressure and/or at higher pH- values. The newdyestuffs are therefore useful for dyeing polyester fibers at the boilin presence of carriers in a wide pH-range, under pressure up to 150 C.and by the Thermosol Process when fixed at 180-230" C.

The dyeings on secondary cellulose acetate and cellulose triacetate havevery nearly the same shade as those on polyester fibers and, further,they show good fastness to pleating and gas fumes and are readilydischargeable.

The dyeings on synthetic polyamide fibers are notable for their good toexcellent fastness to washing.

In the following examples the parts and percentages are by weight andthe temperatures in degrees centigrade.

Example 1 17.25 parts of l-amino-Z-chloro-4-nitrobenzene are diazotizedin the normal way with 25 parts of 30% hydrochloric acid and 6.9 partsof sodium nitrite. Meanwhile l4.5 parts of 1.3- indandione are dissolvedin 200 parts of water and 8 parts of 30% sodium hydroxide solution sothat the solution reacts weakly alkaline: this solution is cooled to 0and the diazo compound is run into it simultaneously with 250 parts of a10% solution of sodium carbonate. On completion of coupling theprecipitated dyestufi is filtered off, washed with water and dried. Itis obtained as yellow powder which dissolves in concentrated sulfuricacid to give orange solutions; on purification from alcohol its meltingpoint is 260-263.

A dyeing preparation is prepared by grinding 1 part of the abovedyestulf with 1 part of sodium dinaphthylmethanedisulfona-te and 8 partsof water in a ball mill and, drying the resulting paste in a spraydrier.

3 parts of this dyestufi? preparation of the above dyestuit are pastedwith a little cold coft water. Cold soft water is run onto the paste andthe dispersion well stirred and added through a sieve to a dyebath of 2parts of lauryl alcohol sulfonate and 4000 parts of water.

100 parts of a scoured fabric of the polyester fiber Dacron (registeredtrademark) are entered in the dye- Patented Get. 20, 1964 r arsaeee bathat 40-50. The temperature is slowly increased and dyeing continued inpresence of parts of an emulsion of a chlorinated benzene in Water for 1to 2 hours at 95-100. The fabric is then rinsed, soaped, rinsed againand dried. It is dyed a yellow shade which is fast to sublimation andheat setting. Wool present in the dyebath is reserved. The yellow dyeingalso possesses good fastness to light, cross dyeing, washing, water, seawater, perspiration and gas fumes and is dischargeable white.

The chlorinated benzene can be replaced by 5 parts of2-hydroxy-1.1'-diphenyl or the dyeing carried out without a carrier at120 in minutes under pressure.

Example 2 The dyestuii described in Example 1 can also be obtained asfollows: 21.4 parts of the sodium salt of 1.3- indandionecarboxylic acidethyl ester are dissolved by boiling for a short time in 300 parts ofacetone with the addition of 30 parts of concentrated hydrochloric acid.The yellow solution formed is cooled to 10 and coupled with the diazosolution prepared as described in Example 1. The precipitated dyestufiis filtered, washed and dried.

In the table below details are given of further examples of indandionedyestuffs which can be produced by the operating procedures of Examples1 and 2. The diazo component has the general formula :I/ I In columns 1,2, 3 and 4 the substituents V, x, y and z are listed, in column 5 thecoupling components and in column 6 the uncorrected melting points ofthe indandione dyestuffs.

All the dyestuffs listed give on Dacron yellow dyeiugs with similarproperties.

Exam- Coupling Melting ple V r 1 2 Component Point, No. degrees 3 011805..- H H 01 1.3-Indandione 279281 4 OEFSO H 01 01 do 265-266 5 011801... H H No: do 298-299 6 OH SOL 01 H NO; do 298 Further usefuldyestuffs according to the invention are the following:

2 (2.5'-dibromo-4' dibromo 4' methylsulfonylphenylazo) 1.3 indandione, 2(2' bromo 4' methylsul-fonylphenylazo) 1.3 indandione and 2 (2'- cyano4' methylsulfonylphenylazo) 1.3 indandione.

Formulae of representative dyes of the foregoing ex- Having thusdisclosed the invention what we claim is: 1. The indandione dye of theformula 3. The indandione dye of the formula 4. The indandione dye ofthe formula References Cited in the file of this patent UNITED STATESPATENTS 1,075,305 Schmidt Oct. 7, 1913 2,339,739 Blackshaw et a1 Jan.18, 1944 2,658,889 Goldberg et a1. Nov. 10, 1953 2,782,186 Merian Feb.19, 1957 2,782,189 Merian Feb. 19, 1957 2,891,943 Marian June 23, 19592,918,344 Jenny Dec. 22, 1959 2,944,871 tkinson July 12, 1960 FOREIGNPATENTS 692,648 Germany June 24, 1940

1. THE INDIANDIONE DYE OF THE FORMULA